Synthesis and thermal decomposition of TNPG

Article abstract of DOI:10.1016/j.tca.2019.178396

1, 3, 5-Trihydroxy-2, 4, 6-trinitrobenzene (TNPG) is an essential energetic intermediate for synthesis of 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB). The thermal stability of TNPG was studied in this work. First, TNPG was synthesized by nitration of

Full text of DOI:10.1016/j.tca.2019.178396

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Synthesis and Thermal Decomposition of TNPG
Wen-qian Wu, Wei Feng, Qiu-han Lin, Shun-yao Wang, Zi-chao
Guo, Li-ping Chen, Wang-hua Chen
PII:
S0040-6031(19)30597-0
https://doi.org/10.1016/j.tca.2019.178396
TCA 178396
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31 August 2019
Please cite this article as: Wu W-qian, Feng W, Lin Q-han, Wang S-yao, Guo Z-chao, Chen
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Synthesis and Thermal Decomposition of TNPG
Synthesis and Thermal Decomposition of TNPG
a
b
a
a
Wen-qian Wu ‧Wei Feng ‧Qiu-han Lin ‧Shun-yao Wang ‧Zi-chao
a, *
a
a
Guo ‧Li-ping Chen ‧Wang-hua Chen
a
Department of Safety Engineering School of Chemical Engineering, Nanjing University of Science
and Technology, Nanjing Jiangsu 210094, China
b
Xi’an Modern Chemistry Research Institute, Xi’an 710065, China

gzc319@njust.edu.cn (Z.C. Guo).
Highlights




TNPG was synthesized and its decomposition process has been thoroughly studied
in this work.
Thermal experiments prove that the decomposition of TNPG follows an
autocatalytic behavior
Kinetic model for TNPG decomposition process was established on the basis of
DSC and ARC results.
This work helps to establish dynamic models for the materials that present coupling
endothermic with exothermic.
【
ABSTRACT】1, 3, 5-Trihydroxy-2, 4, 6-trinitrobenzene (TNPG) is an essential energetic
intermediate for synthesis of 1, 3, 5-Triamino-2, 4, 6-Trinitrobenzene (TATB). The thermal stability
of TNPG was studied in this work. First, TNPG was synthesized by nitration of 1, 3, 5-
trihydroxybenzene with the solution feeding. Then, the thermal stability of TNPG was studied by
DSC and ARC experiments. The non-isothermal DSC results indicated that the thermal
decomposition of TNPG overlapped with the endothermic melting process. The isothermal DSC
and ARC results evidenced that the decomposition of TNPG followed the autocatalytic mechanism.
Two different models were constructed to depict the decomposition process of TNPG. By
comparison with the isothermal DSC results, it was found that the following model could better
describe the decomposition process of TNPG: A→B (autocatalytic), A→Aliq (melting), Aliq→B
S
1

Synthesis and Thermal Decomposition of TNPG
(autocatalytic).
【Keywords】Nitrification; thermal decomposition; coupling; autocatalysis; kinetics
1
. Introduction
1
, 3, 5-Trihydroxy-2, 4, 6-trinitrobenzene (TNPG), a light yellow powder, is a
strongly acidic compound and highly soluble in water. It can form metal salts that have
strong combustion or explosive properties, for example, lead trinitrophloroglucinate is
an important primer [1, 2]. Because its molecular structure contains three hydroxyl
groups and three nitro groups, it is also an important explosive.
TNPG, as an insensitive and high-energy explosive intermediate, can achieve non-
chlorination production of TATB [3-7], reduce production costs and improve the safety
of experiments and production. In recent years, researchers have also developed
insensitive high-energy explosives with eutectics that is formed from TNPG with high-
nitrogen substances or basic compounds [8, 9] in the field of high-energy eutectic.
A large number of research works have been contributed to optimize the synthesis
conditions for TNPG, including reaction temperature, material ratio, concentration, etc.
There are also some reports aimed to study the relationship between structure and
performance of TNPG [10-14]. However, the decomposition features of TNPG have not
been thoroughly studied, which is crucial for storage and transportation of TNPG. In
this work, TNPG will be first synthesized by nitration of phloroglucin with
NH
4
NO
3
/H
2
SO system. Formation of TNPG are confirmed by FTIR and NMR tests.
4
Then thermal analysis technology, say DSC and ARC, combined with thermal analysis
software will be employed to study the decomposition features of TNPG.
2
. Experiment and equipment
2
.1. Reagents
Phloroglucinol (purity≥99%) was purchased from Maclean Biochemical
Technology Co. in Shanghai, Ltd. Concentrated sulfuric acid was purchased from
Shanghai Pharmaceutical Reagent Company of China Pharmaceutical Group
(concentration 98%), A.R. Ammonium nitrate (AN), L.P.
2
.2. Synthesis process of TNPG by phloroglucin nitration
2

Synthesis and Thermal Decomposition of TNPG
TNPG is synthesized by nitration of phloroglucinol with NH
4
NO
3
/H
2
SO system.
4
The synthesis route is as follows (Fig.1). The detailed synthesis procedure can be found
in the Supplementary Profile.
OH
OH
O2N
HO
NO2
OH
AN+H SO4
2
HO
OH
NO2
Fig. 1. The process of phloroglucin nitration
2
.3. Equipment and characterization methods
2
.3.1. Sample and equipment
Before the further study, the synthesized TNPG were tested by TG-DSC to
determine the weight percent of crystal water. The result can be found in the
Supplementary Profile (Fig. S3). About 2.25% weight percent of crystal water was
confirmed in the synthesized TNPG. The mole ratio of TNPG to water is about 3:1.
NICOLETIS10 Fourier infrared spectrometer, AVANCE III 500MHz NMR
spectrometer are used to characterize the structure of TNPG. Differential scanning
calorimeter DSC 1 from Swiss METTLER TOLEDO and the esARC adiabatic
calorimeter from the THT Company are used to study its thermal decomposition.
2
.3.2. Differential scanning calorimetry DSC
The test uses a closed high-pressure stainless steel crucible (HP steel) withstand
pressure of 15 MPa. For the dynamic experiment, the sample is heated from 80-380 °C
under the different temperature rise rates as 1, 2, 4, 8 K/min respectively. The
atmosphere is nitrogen with a flow rate of 50 ml/min. In addition, the temperature for
isothermal experiment are 145, 148, 150, 161, 163, 165 °C (that is, the furnace
temperature can rise to the desired value at temperature rise rate of 200-300 K/min
under program control, then put the sample into furnace and start the test).
2
.3.3. Adiabatic calorimetry ARC
During the test, the prepared sample ball is heated to a preset initial temperature
under adiabatic conditions. After a certain waiting time, the system achieves thermal
balance. Once the sample begins to exothermic, the experimental system automatically
3

Synthesis and Thermal Decomposition of TNPG
enters the strict adiabatic condition.
The sample cell used in this test was made by Hastelloy, and the test conditions
are listed in Table 1. The thermal inertia factor φ is calculated by the following equation,
M c
cell p,cell

=1+
(1)
Msamplecp,sample
Where M represents the mass, c is the heat capacity.
p
Table 1 The test conditions of ARC
Temperature
waiting
Temperature(°C)
50-400
Sensitivity(°C/min)
0.02
m
s
(g)
mball (g)
step(°C)
5
time(min)
10
0.198
15.826
3
. Results and discussion
3
.1. Structural characterization of TNPG
The infrared spectrum of the product is tested as shown in Fig. S1. The H-NMR
and C-NMR spectrum are shown in Fig. S2. These results confirmed the formation of
TNPG. The yield of TNPG was calculated to be about 93%.
3
.2. The DSC test results
3
.2.1. Differential scanning calorimetry DSC
The dynamic DSC results are shown in Fig. 2 and summarized in Table 2.
Obviously, TNPG is a material that has overlapping endothermic and exothermic
processes during heating. The endothermic peaks at about 160 °C correspond to the
melting process of TNPG [12] and the exothermal peaks are the thermal decomposition
process. It is obvious that the exothermic signal is sharp and narrow, indicating that the
exothermic process may be autocatalytic [15-18]. The average specific heat release at the
four temperature rise rates is 3003 J/g. In fact, as shown in Fig. S3 in the Supplementary
o
Profile, there is an endothermic process at about 100~120 C, which corresponds to the
loss process of the crystal water. This endothermic process is not illustrated in Fig. 2.
4

Synthesis and Thermal Decomposition of TNPG
Fig. 2. Dynamic DSC curves of TNPG at 1, 2, 4, 8 K/min
Table 2 Thermal decomposition characteristic parameters of TNPG
β(K/min)
m(mg)
0.82
T
endo(oC)a
158.6
159.1
160.5
162.5
∆Hendo(J/g)
135
T
onset(oC)
T
p
(oC)
∆H (J/g)
d
1
2
4
8
174.9
177.3
187.1
200.1
180.0
188.8
199.8
211.2
-2403
-2912
-3224
-3473
0.83
152
0.84
123
0.82
96
a
T
endo refer to the peak temperature of the endothermic process.
.2.2. Isothermal experiment
The most straightforward way to verify the autocatalytic process is to conduct the
3
isothermal experiments [16]. Different temperature below and above the melting point
are selected for isothermal experiments respectively. The results are shown in Fig. 3.
The heat flow profiles in Fig. 3(a) evidence that TNPG can decompose in the solid state
because the isothermal temperatures in this figure are below the melting point. The heat
flow profiles in Fig. 3(a) present “Bell” shape, indicating that the decomposition of
TNPG in the solid state presents autocatalytic behavior [16-21]. The induction periods
gradually reduce with the isothermal temperature increasing.
Since the isothermal temperature in Fig. 3(b) is higher than the melting point, the
exothermic signals correspond to the decomposition process of TNPG in the liquid state.
Obviously, since the heat flow profiles in Fig. 3(b) present the “Bell” shape, the
decomposition process in the liquid state presents autocatalytic nature.
Moreover, from the dynamic DSC experiment, the decomposition process in liquid
state is more intense and the decomposition rate is different from the solid state, so the
heat release rate increases sharply and causes occurrence of “spikes”. At the same time,
the consistence of two phases and purity of the substance resulting the unsmooth curves.
5

Synthesis and Thermal Decomposition of TNPG
(a) The curve below the melting point
(b) The curve above the melting point
Fig. 3. The isothermal curves at different temperature
3
.3. Adiabatic calorimetry test-ARC
To further investigate the thermal decomposition behaviors of TNPG, adiabatic
calorimetry tests by ARC were conducted. The temperature and pressure profiles are
shown in Fig.4 and the thermal decomposition parameters obtained are summarized in
Table 3. From Fig. 4(a), the sample begins to decompose at about 150 °C, and as the
temperature increases, the pressure during the decomposition gradually increases like
Fig. 4(b). After about 30 minutes, the temperature and pressure rise sharply. The
temperature drastically increased from 156 °C to 184 °C in three minutes and the
corresponding pressure increased from 4.5 bar to 25 bar. This violent temperature
increase is consistent with the sharp heat flow profiles of DSC tests.
In addition, the onset exothermic temperature (T ) is 150 °C. This temperature is
0
obviously lower than the melting point of TNPG, indicating that the decomposition
process of TNPG could occur in the solid state. This result is in agreement with the
isothermal DSC results in Fig. 3(a).
From Table 3, one can see that the value of the thermal inertia factor φ is as high
as 17.78. The kinetics determined in this condition is unreliable. Therefore, the kinetic
model and kinetic parameters will be calculated using the DSC results.
6

Synthesis and Thermal Decomposition of TNPG
(a) Temperature-time and pressure-time curve
(b) Pressure-temperature curve
(
c) Temperature rise rate-time curve
Fig. 4. The ARC test results for TNPG
Table 3 The thermal decomposition characteristic parameters of TNPG
(d) Temperature rise rate-temperature curve
T
0
(°C)
(dT/dt)
0
T
max (°C)
(dT/dt)max
(dP/dt)max
P
max (bar)
φ
∆Tad (°C)
150.5
0.13
184.5
194.32
592.77
25.14
17.78
33.9
3
.4. Kinetic analysis
3
.4.1. Calculation of E and A
Before constructing the kinetic model, the initial value of activation energy (E)
was calculated by Friedman [16] and Kissinger methods [17] respectively. The Friedman
method was first used to observe the relationship between the activation energy E and
the conversion α and judge whether the decomposition in the liquid state can be
described by a single reaction. Then the value of activation energy was calculated by
Kissinger method.
Using the Friedman method, reliable activation energy can be obtained without
involving the mechanistic function. Equation (2) is the Friedman equation, from which
the value of activation energy E at each reaction conversion α can be obtained [22-26]
.
In [β (dα/dT)] = In [f (α) A]-E/RT (2)
α
Where β is the temperature rise rate, K/min; α is conversion; A is the pre-
7

Synthesis and Thermal Decomposition of TNPG
-1
exponential factor under the reaction conversion α, s ; f(α) is the mechanism function;
E is the activation energy，kJ/mol; R is the ideal gas constant, 8.314 J/mol·K；T is
temperature, K.
The relationship between the E and α calculated by the Friedman method is shown
in Fig. 5. We can see that within the conversion range from 0.1 to 0.9, there is no
obvious fluctuations and the value of average E is about 97-103 kJ/mol, indicating that
the thermal decomposition process in the liquid state can be described by one single
reaction.
The Kissinger method considers that the reaction rate is the highest at the peak
temperature Tmax of the heat flow curve, and the non-isothermal and heterogeneous
kinetic equation can be rewritten to the equation (3):
In (β/Tmax2) =In (RA/E)-E/RTmax
(3)
Where β is the temperature rise rate, K/min; α is conversion; A is the pre-
-1
exponential factor, s ; E is the activation energy, kJ/mol; R is the ideal gas constant,
.314 J/mol·K.
max is obtained by a set of curves of TNPG at four temperature rise rates in Fig.2,
8
T
and then a curve of In (β/Tmax2) vs 1/Tmax is obtained. The activation energy E and pre-
exponential factor A is calculated from the slope and intercept from the fitted curve [23-
27].
The experimental data was fitted using the Kissinger method and the results are
shown in Fig. 6. The activation energy of the reaction is 113 kJ/mol, and the
-1
corresponding pre-exponential factor lgA is 8.8683 s . The result shows the activation
energy of TNPG decomposition calculated by the Friedman method and the Kissinger
method are similar.
Fig.5. Relationship of E and α
Fig.6. Fitting results of Kissinger method
3
.4.2. Construction of reaction model
In this section, two reaction models will be constructed to depict the thermal
behaviors of TNPG decomposition. The Thermal Safety Software (TSS) developed by
8

Synthesis and Thermal Decomposition of TNPG
St. Petersburg Chemical Information Company [27-29] is used to establish the reaction
model and fit the kinetic parameters.
Model 1- construction reaction model with exothermal data
Based on the previous results, the decomposition of TNPG in liquid state can be
depicted by one single reaction that presents strongly autocatalytic behavior. The
traditional SB model ignores the initial stage of the autocatalytic reaction. Herein, the
autocatalytic model including the initial reaction was employed as follows:
A→B (initial stage)
A+B→2B (autocatalytic stage)
Then its kinetic expression can be described as：
r
1
=A
1
Pm·exp (-E
1
/RT) · (1-α) n1
(4)
(5)
Pm·exp (-E
/RT) ·α · (1-α)
n21
n22
r
2
=A
2
2
m
n1
/RT)+αn2 )
dα/dt = r
1
+r
2
=A
0
P ·exp (-E/RT) ·(1-α) ·(Z
0
·exp(-E
Z
(6)
m
Where P is the influence of the pressure on reaction mechanism, but it is ignored
in the simulation of TSS. The superscript of m in equation (4) is the reaction order of
P. Z
0
= (A
1
/A
2
) is an autocatalytic factor, and E is the difference between the activation
Z
energy of the initial stage and the autocatalytic stage. The simulation results are shown
in Fig.7 and Table 4.
(a) Curve of heat release and time
(b) Curve of heat release rate dQ/dt and time
Fig.7. Simulation and experimental curves of model 1
Model 2- construction reaction model with exothermic overlapping with melting
As evidenced by the isothermal DSC and ARC results, the exothermic
decomposition can occur in the solid state of TNPG. The construction of the model 2
considers the endothermic melting process and the decomposition processes in both the
solid and liquid states. The reaction model is constructed as follows.
A→B
=A1, 0 Pm exp (-E/RT) (1-α
A→Aliq (melting) T =0; T
liq→B (autocatalytic)
S
(autocatalytic)
r
1
1
) n1· (Z0, 1exp (-E
≥T : r =U (T
Z
/RT) +α
i
n2)
(7)
(8)
n1
n2 n3
e
<Tf:
r
f
e
f
f
s
e
-T
f
) (1-α )
A
9

Synthesis and Thermal Decomposition of TNPG
n2
r
2
=A2，0Pm·exp (-E/RT) α
Where A→B
2
n1·(Z0,2exp(-E
Z
/RT)+α
2
)
(9)
S
represents the autocatalytic decomposition process in the solid
phase; A→Aliq is the melting process [28-31], according to the dynamic DSC test, the
change of melting peak with temperature rise rate is not very obvious and it just a
physical reaction; Aliq→B is the autocatalytic decomposition process in liquid phase.
In equation (8), T
e
is the environment temperature, T
f
is the melting point of TNPG, r
f
is the reaction rate of melting, and U
s
is the heat transfer coefficient between TNPG and
environment. The model parameters are obtained by fitting with the dynamic DSC data.
The simulation results are shown in Fig. 8 and Table 4.
(a) Curve of heat release and time
(b) Curve of heat release rate of dQ/dt and time
Fig.8. Simulation and experimental curve of model 2
Comparison of the two models
Combined with the above simulation results, the relevant parameters of the
constructed model are shown in Table 4. The value of Q corresponding to the
decomposition process in the liquid state for model 2 is smaller than that of model 1
due to the influence of melting. Although the amount of heat of melting is small, it is
not negligible. The simulation value of E for model 2 is closer to the value calculated
using Friedman method. The model 2 is more in line with the decomposition of the
entire process of TNPG. Model 1 only describes the decomposition process in liquid
state. We cannot determine the real onset decomposition temperature for the
decomposition process in the liquid state due to the thermal coupling effect that may
cause large deviation with the real kinetics.
Table 4 The parameters of different reaction models
model 1
A→B
model 2
model
A→B
s
A→Aliq
Aliq→B
In(A
0
) (In1/s)
(2.57±0.36)×101
(1.16±0.16)×102
7.85±3.64
-
-
(2.24±0.36)×101
(1.01±0.16)×102
E(kJ/mol)
(2.03±0.02)×102
1
0

Synthesis and Thermal Decomposition of TNPG
n
n
1
2
=1.18±0.14
=1.15±0.14
n
n
1
2
=1.68±0.14
=1.26±0.14
n
n
n
1
2
3
=1.93±0.14
n
n
1
2
=1.35±0.14
=1.70±0.14
n
=1.06±0.05
=1.48±0.14
In(Z
0
)
-3.88±0.32
-1.42±2.00
-3.88±0.32
9.87±2.00
-
-
-0.19±0.32
8.97±2.00
E
z
Q (kJ/kg)
(2.83±0.14)×103
(2.80±0.14)×102
(-
(2.72±0.14)××103
7
.44±0.14)×101
U
S
(W/K)
-
-
-
-
(1.26±0.01)×10-
-
-
4
Tf (°C)
(1.56±0.04)×102
3
.4.3. Verification of kinetic models
In order to verify the model 2 is suitable, the above two models are used to predict
the process at different isothermal temperatures, say 161, 163 and 165 °C respectively
and compare the prediction data with the experimental data. The results are shown in
Fig. 9 and Table 5.
(a) Tiso=161 °C
(b) Tiso=163 °C
(c)
Tiso=165 °C
Fig. 9. Comparison between prediction and experiment data for isothermal condition
Table 5 Comparison of data between two models for predicting isothermal experiments
1
1

Synthesis and Thermal Decomposition of TNPG
Sim-Model 1
t(s)a (J/g)b
∆H
Sim-Model 2
∆t(s) ∆H
-2633
Experiment
∆t(s) ∆H
-1112
Tiso(°C)
∆
d
d
(J/g)
d
(J/g)
1
1
1
65
63
61
7889
9095
-2800
-2780
-2750
6595
7529
8539
6995
7577
8899
-2634
-2612
-1254
-1718
10553
a
∆
t refer to the time from the initial decomposition to the end.
refer to the total specific heat production.
Comparing the prediction results of the two models, the values of ∆t and heat
b∆
H
d
release rate predicted by Model 2 is closer to the experiment data. This indicates that
the decomposition processes in Fig.9 are influenced by the decomposition in the solid
state and the melting process. In addition, by comparison of the heat flow profiles in
Figs. 7 and 8, the model 2 can better describe the dynamic DSC data. Therefore, model
2
is more suitable for describing the thermal decomposition overlapping with melting
process of TNPG.
4
. Conclusions
(1) From the view of inherent safety, the solution feeding instead of traditional
solid feeding reduces the risk of the entire reaction process, and the product formation
was identified by related structural characterization technique.
(
2) The DSC dynamic experiment indicates that TNPG is a material overlapped
exothermic with endothermic, which has a high onset decomposition temperature about
74-200 °C and the average specific heat release about 3003 J/g. Moreover, it shows
1
that the decomposition of TNPG may be autocatalytic process, and this property is
further proved in the isothermal and ARC test.
(3) For the kinetic calculation of TNPG, the activation energy calculated by
Friedman method and Kissinger method are similar, respectively 97-103 kJ/mol and
-1
1
13 kJ/mol. The corresponding pre-exponential factor lgA is 8.8816 s .
(4) Considering the autocatalytic decomposition model with initial stage and
effects of melting on the decomposition, the TSS software is used to construct the
mechanism function. It is found that the autocatalytic model 2 including the melting is
closer to the actual situation of TNPG decomposition. For substances with obvious
endothermic coupling with exothermic, the exothermic data should not be used to solve
the reaction function. At the same time, it also provides a reference for the late kinetic
prediction based on reaction model.
Acknowledgments
This work is financially supported by National Key R&D Program of China (2017YFC0804701-4)
1
2

Synthesis and Thermal Decomposition of TNPG
and the Fundamental Research Funds for the Central Universities (30917011312).
References
[
1] L. Y. Zhang, J. L. Huang, Q. Ma. Study of synthesis technologic optimization and performance
of 1, 3, 5-Trihydroxy - 2, 4, 6-trinitrobenzene [C]. China academic journal electronic
publishing house. (2011) 181-184.
[
[
[
[
[
[
[
2] L. Y. Zhang, J. L. Huang, Q. Ma. Investigation on preparation technology and process scale-up
of TNPG [C]. China academic journal electronic publishing house. (2013) 72-75.
3] X. M. Ma, B. D. Li, C. X. Lu, et.al. Synthesis and thermal decomposition kinetics of TATB
without chloride [J]. Journal of explosive and propellants, 32(6) (2009) 24-27.
4] Y. Y. Wei. Preparation of 1, 3, 5-triamino-2, 4, 6-trinitrobezene [J]. Journal of applied chemistry,
(1) (1990) 70-71.
5] Y. Y. Wei. A new method for the preparation of DATB, TATB and their intermediates [J].
Armamentarii Acta, 13(2) (1992) 79-81.
6] B. T. Li, Y. M. Liang. Preparation and characterization of high-pure TATB [J]. Journal of
energetic materials, (2) (1993) 6-11.
7] Z. Lu, J. D. Yi, Y. S. Qiu. Study of TATB on reducing chlorine content [J]. Journal of explosive
and propellants, (4) (1996) 9-11.
8] P. R. Bowden, P. W. Leonard, J. P. Lichthard, et al. Energetic salt of trinitrophloroglucinol and
melamine [C]. Biennial Aps Conference on Shock Compression of Condensed Matter. 19th
Biennial APS Conference on Shock Compression of Condensed Matter, 2017.
9] M. Schmitt, P. Bowden, G. Avilucea et al. Investigation of energetic salts of
trinitrophloroglucinol [C]//. Aps Shock Compression of Condensed Matter Meeting. APS
Shock Compression of Condensed Matter Meeting Abstracts, 2017.
[
[10] W. F. Liu. V. P. Sinditskii and V. Y. Egorshev. Study on the burning velocity of lead
trinitrophloroglucinate [J]. Journal of initiators and pyrotechnics, (3) (2003) 34-35.
[11] G. Y. Zhang, L. Yang, Z. N. Zhou, et.al. Dissolution properties of trinitrophloroglucinol
dissolved in deionized water [J]. Journal of energetic materials, 20(1) (2012) 83-85.
[12] H. Y. Chen, T. L. Zhang, J. G. Zhang, et.al. The preparation, structures and thermal
decomposition mechanisms of Trinitrophloroglucinolhydyate [J]. Journal of initiators and
pyrotechnics, (2) (2005).
[
13] L. Y. Zhang, J. L. Huang, Q. Ma, et.al. Improvement of synthesis technology of TATB free
from chloride [J]. Journal of energetic materials, 20 (5) (2012) 551-554.
[
14] L. Wang, H. Chen, T. Zhang, et al. Synthesis, characterization, thermal and explosive properties
of potassium salts of trinitrophloroglucinol [J]. Journal of hazardous materials, 147(1) (2007)
576-580.
1
3

Synthesis and Thermal Decomposition of TNPG
[
16] S. Vyazovkin, A. K. Burnham, M. José, Criado, et al. ICTAC kinetics committee
recommendations for performing kinetic computations on thermal analysis data [J].
Thermochimica Acta, 520(1-2) (2011) 1-19.
[
[
[
[
[
17] H.E. Kissinger. Reaction kinetics in differential thermal analysis [J]. Analytical Chemistry, 29
(11) (1957) 1702-1706.
18] S. Chervin, G. T. Bodman. Phenomenon of autocatalysis in decomposition of energetic
chemicals [J]. Thermochimica Acta, 392(2002) 371-383.
19] J. C. Oxley, J. L. Smith, E. Rogers, et al. Ammonium nitrate: thermal stability and explosively
modifiers [J]. Thermochimica Acta, 384(1) (2002) 23-45.
20] B. D. Leila, F. Hans. Autocatalytic decomposition reactions, hazards and detections [J]. Journal
of hazardous materials, 93(2002) 137-146.
21] R. Bertrand, H. Marco, F. Patrick, et al. Kinetic analysis of solids of the quasi-autocatalytic
decomposition type: SADT determination of low-temperature polymorph of AIBN [J].
Thermochimica Acta, 665 (2018) 119-126.
[
22] B. Roduit, M. Hartmann, P. Folly, et al. Prediction of thermal stability of materials by modified
kinetic and model selection approaches based on limited amount of experimental points [J].
Thermochimica Acta, 579(2014) 31-39.
[
23] H. L. Peng, L. P. Chen, G. B. Lu, et al. Thermal decomposition kinetics of Urotropin [J]. Journal
of energetic materials, 24(5) (2016) 497-502.
[
24] T. Yang, L. P. Chen, W. H. Chen, et al. Experimental method on rapid identification of
autocatalysis in decomposition reactions [J]. Physical and Chemistry Acta, 30(7) (2014) 1215-
1222.
[25] Y. Y. Chen, L. P. Chen, W. H. Chen, et al. Thermal decomposition characteristic and kinetics
of nitro guanidine solution[J]. Journal of energetic materials, 25(03) (2017) 91-95.
[26] C. X. Zhang, G. B. Lu, L. P Chen, et al. Two decoupling methods for non-isothermal DSC
results of AIBN decomposition [J]. Journal of hazardous materials, 285(2015) 61-68.
[27] S. J. Shen, S. H. Wu, J. H. Chi, et al. Thermal explosion simulation and incompatible reaction
of dicumyl peroxide by calorimetric technique [J]. Journal of Thermal Analysis and
Calorimetry, 102(2) (2010) 569-577.
[
[
[
28] A. Kossoy, T. Hofelich. Methodology and software for assessing reactivity ratings of chemical
systems [J]. Process safety progress, 22(4) (2003) 235–240.
29] Thermal Safety Software(TSS), ChemInform Saint Petersburg(CISP) Co., Ltd. St. Petersburg,
Russia,2017.
30] B. Roduit, M. Hartmanna, P. Follyb, et al. Parameters influencing the correct thermal safety
evaluation of autocatalytic reaction [J]. Chemical engineering transactions, 31 (2013).
1
4

Synthesis and Thermal Decomposition of TNPG
[31] S. Y. Wang, A. Kossoy, Y. D. Yao, et al. Kinetics-based simulation approach to evaluate thermal
hazards of benzaldehyde oxime by DSC tests [J]. Thermochimica Acta, 655(2017) 319-325.
1
5